Disiloxane ester ethers



United States Patent 2,909,"sfs 1' DISILOXANE ESTER ETHERS William J. Shibe, .lr.,'Riverton, N.J., assign or'to R. M.

Hollingshead Corporation, Camden, N. -J., a corporation of New Jersey Application August 20, 1956, Serial No. 605,034

12 Claims. (c1. 260 4483 larly useful as thickening agents for silicate ester fluids in which X is cn cn br'cn cmcn and R is an alkyl radical having from three to ten carbon atoms. The alkyl radicals comprising R may be alike or unlike. The position on the benzene 'ring may be ortho, meta or para as indicated by the lines-extending inside the benzene ring. y

Compounds corresponding to the above are prepared according to the present invention by forming the dialkanol ether of a dihydroxy benzene '(catechol, resorcinol or hydroquinone),'converting the dia-lkanol ether thus obtained to -a simple silicate ether, and then converting the simple silicate ether to an ester ether in which the outer alkyl groups have from 3 to 10 carbons. The individual steps for specific examples of the process of this invention are hereinafter set forth in detail.

EXAMPLE 1 Step 1.Preparation of dialkariol ether of 'dihydroxy benzene 114 grams of hydroquinone are dissolved in one liter of water containing 115 grams of KOH. This material is placed in a round-bottom flask equipped with an agitator, a dropping funnel and a reflux condensers 177 grams of ethylene chlorohydrin are then added to the flask contents, dropwise, with agitation. The batch is then refluxed for two hours and allowed to cool. The product, hydroquinone diethanol ether, is separated out as a crystalline material, and is further purified by recrystallizing from a one n-KOH solution.

' decolorized with fullers earth.

'2 Step 2.-Preparation of a simple silicate ether from the dialkanol ether of Step 450 grams of ethyl silicate areplaced in a round-bottom flask equipped with a high speed. agitator. with a mercury seal and a 30" packed column with a condenser. 198 grams of hydroquinone diethanol ether are then added to the contents of the flask. 5 mls. of la 10% solution of sodium methoxide are then added as a catalyst. The batch is then agitated and slowly brought up to C. Two moles of ethanol are removed from the reaction mixture through the column and the flask contents are stripped under reduced pressureto remove any unreacted ethyl silicate.

Step 3.Transesterificati0n of simple silicate ether to I higher disiloxane ester ether 580 grams (6.6 moles) of secondary amyl alcohol are added to one mole of the simple silicate ether of Step 2. 5 mls. of a 10% solution of sodium methoxylate in methanol is then added using the equipment described in Step 2, and, with vigorous agitation, the reaction mixture is brought tothe boil. Six moles of ethanol (275 grams) are removed in this step through the column. 'The reaction mixture is then stripped of 'any unreacted low boilers such as amyl alcohol or methanol. The reaction mixture is then washed with waterto remove the catalyst. It' is'then dried 'with anhydrous magnesium sulfate and The final product obtained by carrying out'the process described above consists of para phenylene dioxy bis (trisecondary amoxy ethoxy silane) which'has the following structural formula: 1

i ta" v $0.11,. O H OSi0 (Maximo-Q0 onzon o-s eo 0,1111

uct, hydroquinone di propanol ether, is represented by the following formula:

HOCHCHzO-O 0112011011 Step 2.-900 grams of tetra 2 ethyl butyl silicate is placed in a round bottom flask equipped as in Step 2 of Example 1. v

212 grams of hydroquinone di propanol ether is then added to the contents of the flask. 5 mls. of a 10% solution of sodium methoxide is then added as a catalyst.

2 moles of 2 ethyl butanol are removed from the reaction mixture through the column after which the reaction mixture is partly distilled under reduced pressure to remove any excess tetra 2 ethyl butyl silicate. The product thus obtained is represented by the following formula:

OOHzCHCzHs 2 5 CH CH 0611201103115 2H5 oomcnmn,

Step 3.--To the product obtained from Step 2, 260 end product, namely para phenylene dioxy bis (tri secgrams or 2-octanol are added and the reaction mixture ondary amoxy ethoxy silane). heated to remove 2 moles of 2 ethyl butanol. The product is then heated under reduced pressure to remove any EXAMPLE 7 unreacted octanol or 2 ethyl butanol. The product is 5 then purified as outlined in Step 3 of Example 1 yielding paraphenylene dioxy bis (di 2 ethyl butoxy, 2 octoxy,

The procedure of Example 6 is carried out starting with one mole (110 grams) of resorcinol.

isopropoxy silane). EXAMPLE 8 EXAMPLE 3 The procedure of Example 6 is carried out starting Step 1.-SameasinExample 2. 10 with one mole (110 grams) of catechol. As shown in Step 2.Sameasin Example 2. the drawing accompanying this application a dihydroxy Step 3.4 moles (520 grams) of 2-octanol are added benzene may be the starting material or the sodium or to the product obtained from Step 2 and the reaction potassium salt of a dihydroxy benzene may be formed. mixture is then heated to remove four moles (408 grams) In the case of direct conversion of the dihydroxy benof 2 ethyl butanol. The product is then heated under Zene to the dialkanol ether the process employs ethylene reduced pressure to remove any unreacted octanol or oxide whereas in the case of the alkali metal salt the 2 ethyl butanol. The product is then purified as outlined process employs either ethylene chlorohydrin or propylin Step 3 of Example 1. The final product consists of ene chlorohydrin. Likewise, in the conversion of the para phenylene dioxy bis (di 2 octoxy, 2 ethyl butoxy, dialkanol ether to a simple silicate ether in Step 2, either isopropoxy silane) and corresponds to the following ethyl silicate or ethyl butyl silicate may be used. Slmlformula: larly, there are a number of alcohols which may be used GH,CHC H CHgClICsHn I 0 0H, CH. C3H cHCH10-sIl-OCHCHIOOCH1CHOSl-CHzCHCIH6 1C1H5CHCH20H 2115 0 I 02115 2115 s c n CHaCHCflu EXAMPLE 4 in carrying out the .transesterification processcf Step 3. Step 1:414 grams of resorcinol are dissolved in one These include the following alcohols and their isomers: liter of water containing 115 grams of KOH. The pro Propanol cedure of Step 1 of Example 1 is then followed to produce utan resorcinol di ethanol ether. Pentanol Step 2.The procedure of Step 2 of Example 2 is fol- HeXaHOl lowed using 198 grams of resorcinol di ethanol ether in Heptano1 place of the hydroquinone di propanol ether of Ex- Octanol ample 2. Nonanol Step 3.-The product obtained from Step 2 of the pres- 1360211101 cut example 15 Processed as m the case of Step 3 of 40 The group of catalysts set forth in Step 2 of the draw- Example 2. ing is repeated in Step 3 for the sake of clarity but in fina1 Product of Example 4 consists of meta actual practice the catalyst selected for use in carrying phenylene (llOXY bis (di 2 ethyl butoxy, 2 octoxy, ethoXy out Step 2 is still present in the proper amount at the time silane), and corresponds to the following formula: Step 3 is performed.

(C H5(l)HCH:0) Sl-O CH1CH7O 0CH,CH OS'i(-0 CHICHCHI), 01H; 0 0 1H5 GHGHC Hu CH H CsH EXAMPLES In lieu of including in a repetitive manner the carrying out of the steps of the process of the present invention as applied to the very large number of variations in separate examples, the various alternative materials have been identified in the specification and in the drawing of the present application with the intent that they be looked upon as constituting examples of the process and of the products obtainable thereby.

Having thus described my invention, I claim: l. Disiloxane ester ethers having the formula:

Step I.ll4 grams of resorcinol are dissolved in one liter of water containing 115 grams of KOH. The procedure of Step 1 of Example 2 is then followed.

Step 2.The procedure of Step 2 of Example 2 is fol- 45 lowed using the product obtained in Step 1 above.

Step 3.The product of Step 2 above is processed according to the procedure of Step 3 of Example 3. The final product of Example 5 is meta phenylene dioxy bis (di 2 octoxy 2 ethyl butoxy isopropoxy silane) and corresponds to the following )3 o R 0x50110 11 omoHCtH" ROSl--OXOQOXOS IOR 111, 311; ()R )11 CIHiCHCHflO-AI-OCHCHIO OCHICHO-SIFOOHZFHQES in which R is an alkyl radical having from 3 to 10 carcm, i 1 hens and X is selected from the group consisting of CH CH and CH CH(CH H H H 2 2 2 3 C 3 2. Paraphenylene (llOXY bis (d1 2 ethyl butoxy, 2 oc- XAMP 6 toxy, isopropoxy silane). Step 1.-One mole grams) of hydroquinone is ParaPhenylefle diQXY bis 2 octoxy, 2 flthyl dissolved in water and placed in a flask as in Step 1 of butoxy, isopropoxy silane).

Example 1. Two moles (44 grams) of ethylene oxide 4. Meta phenylene dioxy bis (di 2 ethyl butoxy, 2 are then added following the procedure of Step 1 of octoxy eihOXY 5. Meta phenylene dioxy bis (di 2 octoxy 2 ethyl butoxy isopropoxy silane).

Example 1. The remaining steps of Example 1 are fol- 6. Paraphenylene dioxy bis (tri secondary amoxy ethoxy silane).

7. In a process for making disiloxane ester ethers having the general formula:

wherein R is an alkyl radical having from three to ten carbons and X is selected from the group consisting of CH CH and CH CH(CH the steps including reacting about 2 moles of ethylene oxide with about 1 mole of a dihydroxy benzene selected from the group consisting of catechol, hydroquinone and resorcinol to form a dialkanol ether of dihydroxy benzene, reacting about one mole of the said dialkanol ether with about two moles of an organic silicate selected from the group consisting of ethyl silicate and ethyl butyl silicate to form a silicate ether, and reacting said silicate ether with a monohydroxy alkanol containing 3 to carbon atoms to form a disiloxane ester ether.

8. In a process for making disiloxane ester ethers having the general formula:

wherein R is an alkyl radical having from three to ten carbons and X is selected from the group consisting of CH CH and CH CH(CH the steps including reacting an alkali metal salt of a dihydroxy benzene selected from the group consisting of catechol, hydroquinone and resorcinol with a chlorohydrin selected from the group consisting of ethylene chlorohydrin and propylene chlorohydrin, the said alkali metal being selected from the group consisting of sodium and potassium, to form a dialkanol ether of dihydroxy benzene, reacting about 1 mole of the said dialkanol ether with about 2 moles of an organic silicate selected from the group consisting of ethyl silicate and ethyl butyl silicate to form a silicate ether, and reacting said silicate ether with a monohydroxy alkanol containing 3 to 10 carbon atoms to form a disiloxane ester ether.

9. The process defined in claim 7 wherein the di-alkanol ether is hydroquinone diethanol ether, the disiloxane ester ether is para phenylene dioxy bis (tr-i secondary amoxy ethoxy silane), the organic silicate is ethyl silicate and the alkanol is secondary amyl alcohol.

10. The process defined in claim 8 wherein the diallcanol ether is hydroquinone di propanol ether, the disilox-ane ester ether is para phenylene dioxy bis (di 2 ethyl butoxy, 2 octoxy, isopropoxy silane), the chlorohydrin is propylene chlorohydrin, the organic silicate is tetra 2 ethyl butyl silicate and the alkanol is 2-octano1.

11. The process defined in claim 8 wherein the dialkanol ether is resorcinol diethanol ether, the disiloxane ester ether is meta phenylene dioxy bis (di 2 ethyl butoxy, 2 octoxy, ethoxy silane), the chlorohydrin is ethylene chlorohydrin, the organic silicate is tetra 2 ethyl butyl silicate and the alkanol is 2-octano1.

12. The process defined in claim 8 wherein the dialkanol ether is resorcinol di propanol ether, the disiloxane ester ether is meta phenylene dioxy bis (di 2 octoxy 2 ethyl butoxy isopropoxy silane), the chlorohydrin is propylene chlorohydrin, the organic silicate is tetra 2 ethyl butyl silicate and the alkanol is 2-octanol.

References Cited in the file of this patent UNITED STATES PATENTS 2,327,053 Marple et a1. Aug. 17, 1943 2,630,446 Gresham Mar. 3, 1953 2,724,698 Kittleson Nov. 22, 1955 2,776,307 Abbott et a1. Jan. 1, 1957 OTHER REFERENCES Volnov et al.: Jour. Gen. Chem. (USSR), vol. 10, pages 550-6 (1940).

Shukis et al.: Jour. Amer. Chem. Soc., vol. 66 (1944), pp. 1461-2.

George et al.: Ibid, vol. (1953), page 987. 

1. DISILOXANE ESTER ETHERS HAVING THE FORMULA: 